It is known to use Group VIII metal carbonyls as catalysts for water gas shift reactions. See U.S. Pat. Nos. 4,226,845 and 4,453,019 and publications cited therein.
Murahashi, et al., "Catalytic Alkyl Group Exchange Reaction of Primary and Secondary Amines", J. Am. Chem. Soc. July 27, 1983, 105, 5002-5011, teaches the use of palladium catalyst for alkyl group exchange reactions of primary and secondary amines and reported that other metal complexes such as Ru.sub.3 (CO).sub.12 gave relatively high conversion of the amines, but in low yields.
Fenton, U.S. Pat. No. 3,726,925 describes the preparation of trialkylamine with a metal catalyst, e.g., ruthenium or osmium and the like.
Goetz, U.S. Pat. No. 4,059,640, teaches the reaction of a tertiary amine with alcohol in the presence of carbon monoxide and without metal catalyst.
Both Jung, et al., Organomets. 1983, 2, 1042-1044; and McEwen, et al., J. Org. Chem. 1983, 48, 4436-4438 teach that palladium black is not the catalyst of choice for transalkylation reactions; palladium black loses activity when reacted woth primary, secondary, and/or tertiary amines.
It is believed that the references cited by Youval Shvo and Richard M. Laine in their paper "Homogeneous Catalytic Activation of C--N Bonds. Alkyl Exchange Between Tertiary Amines" (J. Chem. Soc. Chem. Comm., Aug. 1980, pp. 753-754) are the nearest known prior art. Among the references listed by Shvo and Laine is the article of Shun-Ichi Murahashi et al., "Palladium Catalyzed Amine Exchange Reaction of Tertiary Amines. Insertion of Palladium (O) into Carbon-Hydrogen Bonds" (J. of the Am. Chem. Soc., v. 100, Jan. 4, 1978, pp. 348-350). This article discloses an attempt to employ a heterogeneous palladium black catalyst for the exchange reaction of tertiary amines. The exchange reactions described proceed with extreme difficulty, requiring a high reaction temperature and long reaction time. We have conducted similarly the suggested heterogeneous palladium black exchange reaction under milder temperature conditions and have met with little success. In this instance, we found that the reaction time became substantially longer with the accompanying slight decrease in reaction temperature, and the amount of catalyst required was unreasonably high for the poor yield obtained.
Further, heterogeneous catalysts are readily deactivated, or poisoned, by a variety of materials including the amines themselves. This, in turn, requires fairly frequent replenishment or regeneration. In practical terms, this means that such heterogeneous catalytic exchange processes are severely limited in their potential commercial application as a means for reproducing mixed tertiary amines or synthesizing other tertiary amines from tertiary mixtures.